Schiff bases derived from phenanthrene-9,10-diamines and orthohydroxy aldehydes

ABSTRACT

Novel Schiff bases are prepared by condensation of phenanthrene9,10-diamines with o-hydroxy aldehydes. The bases can be chelated with metals to form compounds useful as yellow pigments.

United States Patent Dhaliwal Sept. 2, 1975 [5 SCHIFF BASES DERIVED FROM2,381,952 8/1945 Gubelmann 260/438.l PHENANTHRENE910 DIAMINES A2,450,276 9/1948 Folger et a1 260/438.l 3,054,824 9/1962 ArrigO260/438.1 X

ORTHOHYDROXY ALDEHYDES 3,687,991 8/1972 Gaeng et al 260/438.1 x

Pritam Singh Dhaliwal, Edison, N.Y.

Inventor:

E. I. Du Pont de Nemours and Company, Wilmington, Del.

Filed: Dec. 8, 1972 Appl. NO.: 313,359

Assignee:

US. Cl....... 260/438.1; 106/288 Q; 260/429 C;

References Cited UNITED STATES PATENTS 5/1938 Schmidt 260/438.1 X

FOREIGN PATENTS OR APPLICATIONS 1,156,922 7/1969 United Kingdom OTHERPUBLICATIONS Calvin et al., J.A.C.S. Vol. 68, pp. 2254-2256 (1946).Barkelew et al., J.A.C.S Vol. 68 pg. 2257 (1946). Index Chemicus, Vol.18, No. 7, 55981 (1965).

Primary ExaminerI-Ielen M. S. Sneed 57] ABSTRACT Novel Schiff bases areprepared by condensation of phenanthrene-9,IO-diamines with O-hydroxyaldehydes. The bases can be chelated with metals to form compoundsuseful as yellow pigments.

4 Claims, No Drawings SCI-IIFF BASES DERIVED FROM PI-IENANTHRENE-9, lO-DIAMINES AND ORTI-IOl-IYDROXY ALDEI-IYDES BACKGROUND OF THE INVENTIONAlthough a number of lightfast organic pigments have been developed inthe blue to green color range, as exemplified by the phthalocyanines,and in the red to violet range, as exemplified by the quinacridones,there has been much less success with the development of such pigmentsin the yellow range. The present invention is directed to the productionof novel yellow organic pigments.

SUMMARY OF THE INVENTION wherein Me is nickel, cobalt or copper and Dand D are as given before.

For the preparation of the Schiff bases and the chelates of theinvention, phenanthrene-9,IO-diamines of 5 the formula:

wherein R is hydrogen, chlorine or bromine, are pre- 20 ferred. Othersubstituents may be present on the phenanthrene moiety, however, forexample, lower alkyl radicals such as methyl and ethyl, and alkoxyradicals such as methoxy.

The o-hydroxy aldehydes that may be employed in- 2 1 H 0 u C NH C-H 2 II N D I I 1 I 52 l n:

I I I N H\ H! I/ I 2 wherein D represents the atomsnecessary to completeclude salicyl aldehyde; 3,5-dibr0moand 3,5- a phenanthrene nucleushaving the indicated nitrogen dichlorosalicylaldehyde; 2,4-dihydroxy-3-atoms attached to the ,9, l 0-positions and D representsformylquinoline; and Z-hydroxy-l-naphthaldehyde. the atoms necessary tocomplete a nucleus of the for- The preferred compound is2,4-dihydroxy-3- mula: 45 formylquinoline which, when condensed with 9 XX a 01. N 0

V y l wherein X is chlorine or bromine.

The metal chelate derivatives have the formula:

,D i Ar Q r N I D B: Me\

is] N o at 1 H I \D2 phenanthrene-9, IO-diamine and chelated yields acompound of the formula:

wherein each R is hydrogen. n

The Schiff bases of this invention are produced by condensing two molesof the o-hydroxy aldehyde'with one mole of phenanthrene-9,IO-diamine ora substituted derivative of the latter. The Schiff base is furtherreacted with a nickel, cobalt or copper salt, such as for example nickelacetate, to give a highly insoluble reddish-yellow compound havingexceptional lightfastness and other valuable pigmentary properties,i.e., to give the chelate.

The condensation of the o-hydroxy aldehyde with thephenanthrene-9,l-diamine can be carried out in a va-' riety of polarsolvents. it is found that the reaction proceeds readily in acidicaqueous medium (pH 3-5), butanol, ehtanol, and dimethylformamide.However, if desired, other solvents such as, for example, propanol,ethylene glycol or the like, may be used with equal success.

The metal complexes can be conveniently formed by reacting the Schiffbase with a metal salt of an organic acid in suspension in ahigh-boiling solvent such as dimethylformamide, dimethylacetamide,dimethylsulfoxide, tetramethylene sulfone and the like. Although forpurposes of illustration nickel acetate is the metal salt used and ispreferred, salts of the metals cobalt or copper may be substituted.Salts other than acetates can be used provided they are sufficientlysoluble in the solvent used in carrying out the chelation reaction.Since the condensation to form the Schiff base can also be carried outin a high-boiling polar solvent such as dimethylformamide or one of theother solvents listed above, the formation of both the Schiff base andthe metal complex can be carried out in succession in the same reactionmedium without isolation of the Schiff base intermediate.

To illustrate in detail the preparation of the compounds of theinvention, the following examples are given. These are intended to beillustrative only and are not to be held as in limitation of theinvention.

EXAMPLE 1 l A. Synthesis of Schiff base from 2,4-dihydroxy-3-formylquinoline and phenanthrene-9, l O-diamine Ten grams ofphenanthrene-9,l0-diamine and 21.5 grams of2,4-dihydroxy-3-formylquinoline are refluxed in 1,800 ml butanol for 5hours. The slurry is filtered hot and the presscake washed with alcoholand dried. The bright yellow Schiff base product weighs 22.5

grams. B. Formation of nickel chelate Fifteen grams of the Schiff baseproduct of A and 10.0 grams nickel acetate tetrahydrate are heated atreflux in 1,800 ml N,N'-dimethylformamide for 4 hours. The slurry isfiltered hot and the presscake washed successively withdimethylformamide, alcohol, and water, and dried at. 60C. The yield ofproduct is 14.6 grams. I

The chelate product is extractedwith 1,000 ml of boilingdimethylformamide for minutes, filtered hot, washed and dried. Thirteenand four-tenths grams of a red-shade yellow product are obtained. Uponanalysis the following are the results:

Calculated for C31H2U 4O4Nl Found Nl 9.7l 9.84 N 9.22 9.03 C 67.21 66.24H 3.29 3.37

This analysis indicates the compound to be the chelate of thestructuralformula given as (V), above, wherein Me is nickel and each Ris hydrogen.

The chelate is reddish-yellow in color and is found to possessoutstanding outdoor durability when used as a pigment.

EXAMPLE 2 A. Synthesis of 3,6-dichloro-phenanthrene-9,l0- diaminedihydrochloride In this synthesis 45.0 grams of3,6-dichlorophenanthrene-9,IO-quinone, 62.5 grams barium carbonate, and56.5 grams hydroxylamine hydrochloride are heated in 4,000 ml ethylalcohol at reflux for 5 hours. The slurry is filtered hot and thepresscake washed with-alcohol. The filtrate is concentrated byevaporation to half its volume, cooled to C. and 260 grams stannouschloride dissolved in 1,200 ml concentrated hydrochloric acid is addedover a 30 minute period, while maintaining the temperature below C. Theslurry is stirred for an additional one-half hour period whilemaintaining the temperature at 70 to 80C., cooled to room temperatureand filtered.

The presscake is washed first with concentrated hydrochloric acid, thenwith water, and dried at room temperature. The yield of white solid is38.5 grams. B. Synthesis of Schiff base from 2,4-dihydroxy-3-formylquinoline and the diamine of A Thirty-eight and one-half grams ofthe product of A, and 46.8 grams of 2,4-dihydroxy-3-formylquino1ine areheated in 4,000 mi of butanol at reflux for 5 hours. The hot slurry isfiltered, the presscake washed with ethanol, and dried. The yield is60.0 grams of a bright yellow solid.

C. Formation of nickel chelate Thirty grams of the bright yellow Schiffbase as prepared in B and 20.0 grams of nickel acetate tetrahydrate areheated under reflux in 3000 m1 dimethylformamide for 4 hours. The slurryis filtered hot and the presscake washed free of nickel salts and dried.The product weighs 24.5 grams.

' The 24.5 grams of product of Care pulverized and extracted withboiling dimethylformamide for 25 minutes, filtered hot, and thepresscake washed until free of nickel salts and dried. A yield of 23.0grams of a redshade yellow product is obtained. Upon analysis, thefollowing results are obtained:

Calculated for C H,,,Cl N,O Ni Found Ni= 8.60 8.89 N 8.29 8.11 C =6].4858.19 H 2.67 2.72 C! 10.51 10.0

This analysis shows that the chelate has a structure corresponding tothat of formula (V), above, wherein Me is nickel and each R is chlorine.

EXAMPLE 3 A. Synthesis of 3,6-dibromo-phenanthrene-9,l0- diaminedihydrochloride Forty-six grams of 3,6-dibromo-phenanthrene-9,l0-quinone, 56.5 grams of hydroxylamine hydrochloride and 62.5 grams ofbarium carbonate are heated at reflux in 2,600 mi ethanol for 5 hours.The slurry is fi1- tered hot and the presscake washed with alcohol. Thefiltrate is heated to 70C. and 250 grams of stannous chloric acid isadded over a 20 minute period with the temperature held at 80C. Theslurry is cooled to room temperature over a 2 hour period and filtered,washed first with hydrochloric acid, and then with water, and dried. Theproduct weighs 52.0 grams.

B. Synthesis of Schiff base from 2,4-dihydroxy-3- formylquinoline andthe diamine of A To carry out the reaction, 26.0 grams of the productobtained in step A and 31.2 grams of 2,4-dihydroxy-3- formylquinolineare heated at reflux for 5 hours in 3,000 ml of butanol. The slurryisfiltered hot and the presscake washed with alcohol and dried. The yieldof product is 40.0 grams.

C. Formation of nickel chelate The 40 grams of product of step B and20.8 grams of nickelacetate are heated at reflux in 3,500 ml.dimethylformamide for 4 hours. The slurry is filtered hot, washed anddried. The yield is 23 grams.

The 23 grams of product from step C is pulverized and extracted with1,700 ml of boiling dimethylformamide for 20 minutes. The slurry isfiltered hot, washed successively with dimethylformamide, alcohol, andwater and alcohol, and dried at 60C. The product is 21.5 grams of ared-shade yellow solid.

Analysis of this product shows the following:

Calculated for C; H,,,Br. ,N O Ni Found Ni 7.59 7.43 N 7.33 7.l4 C=53.40 52.07 H 2.35 2.48 Br 20.95 l8.9

This analysis shows the chelate has a structure corresponding to that offormula (V), above, wherein Me is nickel and each R is bromine.

EXAMPLE 4 Analysis of this product shows:

Calculated for C ,;H- N 2 Found C 83.72 82.04 H 4.65 4.59 N 5.42 5.84

B. Formation of nickel chelate One gram of the product of A and 0.6 gramof nickel acetate tetrahydrate are heated in 100 ml of dimethylformamideat reflux for 4 hours. The slurry is filtered hot, washed, successivelywith alcohol, water, and alcohol, and dried at 60C. The yield of chelateis 0.99

gram.

EXAMPLE 5 Preparation of the chelate of Example 1 without isolation ofthe Schiff base To carry out the reaction, 400 ml of dimethylformamide,2.3 grams nickel acetate tetrahydrate and 3.0 grams2,4-dihydroxy-3-formylquinoline are heated at reflux for 1 hour. Afterone hour, 2.0 grams phenanthrene-9,l0-diamine dihydrochloride is added,and the reflux continued for an additional three and one-half hours.Immediately upon addition of the phenanthrene- 9,lO-diaminedihydrochloride a reddish-yellow solid precipitates out of solution. Atthe end of the reflux period, the slurry is filtered hot, washed withalcohol, then with water and alcohol, and dried at C. The yield of theproduct is 2.2 grams.

EXAMPLE 6 For C ,.H,,,N. ,O. ,Br Ni, analysis shows:

Found Calculated N|= 7.0] 7.35 N 3.65 3.55 C =44.6 42.75 H 1.95 1.77Br=37.3 40.6

This example shows the formation of the tetrabromosubstituted chelate.The corresponding chlorosubstituted chelate can be prepared by simplemolar substitution of 3,5-dichlorosalicylaldehyde for 3,5-dibromosalicylaldehyde.

What is claimed is:

l. A metal chelate of structural formula:

wherein Me is nickel, cobalt or copper and wherein D represents theatoms necessary to complete a phenanthrene nucleus having the indicatednitrogen atoms attached to the 9,l0-positions and D represents the atomsnecessary to complete a nucleus of the formula A Y N I 3 [a] E l I Owherein X is chlorine or bromine.

2. A metal chelate of claim 1 wherein D represents the atoms necessaryto complete a nucleus of the formula: X X

wherein X is chlorine or bromine.

4. A metal chelate of claim 1 wherein D represents vthe atoms necessaryto complete a nucleus of the formula:

3. A metal chelate of'claim 1 wherein D represents the atoms necessaryto complete a nucleus of the formula: l

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTIGN PATENT NO. I 3 903118 DATED 3 September 2, 1975 INVENTOR(S) Pritam Singh Dhaliwal It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

Claim 1, Columns? and 8, lines 1 threugh 8,

delete replace "9 r' with -or-=, replace with and delete d cl 1 d hEngnc an Sea 6 t 15 twenty-seventh D y f January 1976 [SEAL] Attest:

RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner of'larentsand Trademarks

1. A METAL CHELATE OF STRUCTURAL FORMULA:
 2. A metal chelate of claim 1wherein D2 represents the atoms necessary to complete a nucleus of theformula:
 3. A metal chelate of claim 1 wherein D2 represents the atomsnecessary to complete a nucleus of the formula:
 4. A metal chelate ofclaim 1 wherein D2 represents the atoms necessary to complete a nucleusof the formula: